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WO2003018214A2 - Films recouverts de peinture - Google Patents

Films recouverts de peinture Download PDF

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Publication number
WO2003018214A2
WO2003018214A2 PCT/EP2002/009104 EP0209104W WO03018214A2 WO 2003018214 A2 WO2003018214 A2 WO 2003018214A2 EP 0209104 W EP0209104 W EP 0209104W WO 03018214 A2 WO03018214 A2 WO 03018214A2
Authority
WO
WIPO (PCT)
Prior art keywords
film
radiation
films
film according
adhesive
Prior art date
Application number
PCT/EP2002/009104
Other languages
German (de)
English (en)
Other versions
WO2003018214A3 (fr
Inventor
Helmut Steininger
Ria Kress
Erich Beck
Rainer Königer
Original Assignee
Basf Aktiengesellschaft
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Priority to US10/485,818 priority Critical patent/US7579082B2/en
Priority to EP02772152A priority patent/EP1419017B1/fr
Priority to AU2002336973A priority patent/AU2002336973A1/en
Priority to DE50206328T priority patent/DE50206328D1/de
Priority to JP2003522718A priority patent/JP4086111B2/ja
Publication of WO2003018214A2 publication Critical patent/WO2003018214A2/fr
Publication of WO2003018214A3 publication Critical patent/WO2003018214A3/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/52—Two layers
    • B05D7/53—Base coat plus clear coat type
    • B05D7/532—Base coat plus clear coat type the two layers being cured or baked together, i.e. wet on wet
    • B05D7/5323—Base coat plus clear coat type the two layers being cured or baked together, i.e. wet on wet the two layers being applied simultaneously
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/02—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber
    • B05D7/04—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber to surfaces of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal
    • Y10T428/31692—Next to addition polymer from unsaturated monomers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31938—Polymer of monoethylenically unsaturated hydrocarbon

Definitions

  • the present invention relates to films which are coated with at least two layers of lacquer, a process for producing the films and their use.
  • EP-A-374551 discloses coated substrates which are suitable for the production of add-on parts for automobile bodies.
  • the coated substrates described in EP-A-374551 consist of metal sheets which are coated with at least one layer of paint or of composite materials whose surface layer consists of the coated metal sheets. From DE-4424290.9-A1 substrates coated with several layers are also known. These are deformed and, if necessary, further processed with the help of further materials. In this way, add-on parts for vehicle bodies can be produced.
  • carrier films A wide variety of materials can be considered as carrier films.
  • Thermal coatings are mostly used to coat the carrier films. Varnishes curable with UV radiation have also been tested. Such are e.g. described in DE 19535935 A1, DE 4439350-A1.
  • the object of the present invention is accordingly to provide films coated with at least two layers of lacquer, which form a useful alternative to the liquid lacquers customary hitherto.
  • the cold and thermoformability (deep drawing) of the films and the color consistency should be ensured.
  • an improved adhesion of the individual lacquer layers is to be achieved.
  • an improvement over the previous state of the art should be achieved with regard to the mechanical strength, in particular with regard to the breaking strength.
  • the paint layers should have a scratch resistance, chemical resistance and comparable to the previous liquid paints
  • the solution according to the invention are foils coated with at least two lacquer layers, in which at least one first lacquer layer, which is radiation-curable, is present on a carrier film, and at least one second lacquer layer is present, which is at least partially curable without exposure to radiation.
  • the second lacquer layer is therefore preferably at least partially thermally curable.
  • the radiation-curable paints are primarily for the first
  • Lacquer layer used. Radiation-curable clearcoats are preferably used. However, it is also possible to color and / or pigment the clearcoats.
  • the clearcoats are curable with high-energy radiation, such as UV radiation or electron radiation, in particular UV radiation
  • Such clearcoats contain at least one radiation-curable oligomeric or polymeric binder as an essential component.
  • the polymers or oligomers used as binders usually have a number average molecular weight of 500 to 50,000, preferably 1,000 to 5,000. They preferably have a double bond equivalent weight of 300 to 2,000, particularly preferably 400 to 900.
  • the formulated binders preferably have a viscosity of 250 to 11,000 mPas at 23 ° C. They are preferably used in an amount of 5 to 50% by weight, preferably 6 to 45% by weight, particularly preferably 7 to 40% by weight, very particularly preferably 8 to 35% by weight and in particular 9 to 30% by weight. -%, each based on the solids of the clearcoat applied.
  • Suitable binders come from the oligomer and / or polymer classes of the (meth) acrylic-functional (meth) acrylic copolymers, Polyether acrylates, polyester acrylates, polyesters, epoxy acrylates, urethane acrylates, amino acrylates, melamine acrylates, silicone acrylates and phosphazene acrylates and the corresponding methacrylates, as described, for example, in German Patent DE 197 09 467 C 1, page 4, line 36, to page 5, line 61 become. It is preferred to use binders which are free from aromatic structural units.
  • Urethane (meth) acrylates, phosphazene (meth) acrylates and / or polyester (meth) acrylates are therefore preferably used, particularly preferably urethane (meth) acrylates, in particular aliphatic urethane (meth) acrylates.
  • the urethane (meth) acrylates are obtained by reacting a di- or polyisocyanate with a chain extender from the group of the diols / polyols and / or diamines / polyamines and / or dithiols / polythiols and / or alkanolamines and then reacting the remaining free isocyanate groups with at least a hydroxyalkyl (meth) acrylate or hydroxyalkyl ester of other ethylenically unsaturated carboxylic acids.
  • chain extenders di- or polyisocyanates and hydroxyalkyl esters are preferably chosen so that
  • Mercaptyl groups is between 4: 1 and 1: 2, preferably between 3: 1 and 3: 2, and
  • the urethane (meth) acrylates by first reacting some of the isocyanate groups of a di- or polyisocyanate with at least one hydroxyalkyl ester and then reacting the remaining isocyanate groups with a chain extender.
  • the amounts of chain extender, isocyanate and hydroxyalkyl ester are chosen so that the equivalent ratio of the NCO groups to the reactive groups of the chain extender is between 4: 1 and 1: 2, preferably between 3: 1 and 3: 2, and that Equivalent ratio of the remaining NCO groups to the OH groups of the hydroxyalkyl ester is 1: 1.
  • all intermediate forms of these two processes are also possible.
  • part of the isocyanate groups of a diisocyanate can first be reacted with a diol, then another part of the isocyanate groups can be reacted with the hydroxyalkyl ester and then the remaining isocyanate groups can be reacted with a diamine.
  • the urethane (meth) acrylates can be made more flexible, for example, by reacting corresponding isocyanate-functional prepolymers or oligomers with longer-chain, aliphatic diols and / or diamines, in particular aliphatic diols and / or diamines with at least 6 carbon atoms. This flexibilization reaction can be carried out before or after the addition of acrylic or methacrylic acid to the oligomers or prepolymers.
  • suitable urethane (meth) acrylates include the following commercially available polyfunctional aliphatic urethane acrylates:
  • the systems listed here are liquid as 100% formulations.
  • the urethane acrylate system we prefer to use is solid in the 100% state.
  • Castable solutions are made on site from the solid resin. Suitable solvents for this include, among others, THF, acetone, MEK and MIBK.
  • Urethane (meth) acrylates containing hydroxyl groups are known, for example, from US Pat. Nos. 4,634,602 or 4,424,252.
  • a suitable polyphosphazene (meth) acrylate is the phosphazene dimethacrylate from Idemitsu, Japan.
  • the clearcoats can be the reactive thinners, photoinitiators and additives, such as light stabilizers, slip additives, polymerization inhibitors, matting agents, defoamers, flow control agents and described in German Patent DE 197 09 467 C 1, page 5, line 62, to page 6, line 30 film-forming aids included.
  • high boilers can preferably be added to the clear coat. Their proportion can be 5% to 60%, preferably 10% to 30%. Dioxane, toluene and ethyl acetate can be used as high boilers, butyl acetate is preferably used.
  • the layer thickness of the clearcoats is 1 ⁇ m to 400 ⁇ m, preferably 5 ⁇ m to 100 ⁇ m, particularly preferably 15 ⁇ m to 60 ⁇ m.
  • the choice of layer thickness depends on the stretching of the film.
  • the minimum layer thicknesses mentioned relate to the end product, i. H. a usually stretched film.
  • the at least partially curable lacquers without radiation are preferably the color-providing layers which at the same time form the topcoat layer.
  • Car refinish paints known from the prior art can also be used here because of their good physical drying properties and their good availability.
  • Suitable refinish coatings are single or multi-component systems.
  • two-component systems contain at least one Compound, especially a binder, with isocyanate-reactive functional groups such as thiol, hydroxyl and primary and secondary
  • Amino groups especially hydroxyl groups, and at least one polyisocyanate.
  • Suitable binders are random, alternating and / or block-shaped linear and / or branched and / or comb-like (co) polymers of ethylenically unsaturated monomers, or polyaddition resins and / or polycondensation resins. These terms are supplemented by Römpp Lexikon Lacke und Druckmaschine, Georg Thieme Verlag, Stuttgart, New York, 1998, page 457, "Polyaddition” and “Polyadditionharze (polyadducts)", and pages 463 and 464, "Polycondensates”, “Polycondensation” and “Polycondensation Resins", as well as pages 73 and 74, "Binders”.
  • Suitable (co) polymers are (meth) acrylate (co) polymers or partially saponified polyvinyl esters, in particular
  • suitable polyaddition resins and / or polycondensation resins are polyesters, alkyds, polyurethanes, polylactones, polycarbonates, polyethers, epoxy resin-amine adducts, polyureas, polyamides, polyimides, polyester-polyurethanes, polyether-polyurethanes or polyester-polyether-polyurethanes, in particular polyester-polyurethanes ,
  • the (meth) acrylate (co) polymers have particular advantages and are therefore used with particular preference. Manufacturing processes for (meth) acrylate copolymers are described in European patent application EP 0 767 185 A 1, German patents DE 22 14 650 B1 or DE 27 49 576 B1 and American patents US 4,091,048 A1, US 3,781,379 A. 1, US 5,480,493 A 1, US 5,475,073 A 1 or US 5,534,598 A 1 or in the standard work Houben-Weyl, Methods of Organic Chemistry, 4th Edition, Volume 14/1, pages 24 to 255, 1961.
  • Reactors for the copolymerization are the customary and known stirred kettles, stirred kettle cascades, tubular reactors, loop reactors or Taylor reactors, as described, for example, in the patents and patent applications DE 1 071 241 B1, EP 0 498 583 A1 or DE 198 28 742 A1 or in the article by K. Kataoka in Chemical Engineering Science, volume 50, number 9, 1995, pages 1409 to 1416.
  • binders in the repair paints can vary widely and depends on the requirements of the individual case. They are preferably used in an amount of 5 to 90% by weight, preferably 6 to 80% by weight, particularly preferably 7 to 70% by weight, very particularly preferably 8 to 60% by weight and in particular 9 to 50% by weight. %, each based on the solids of the refinish applied.
  • the polyisocyanates can have aliphatic, cycloaliphatic or aromatic basic structures. However, at least two of these basic structures can also be present in a polyisocyanate.
  • a polyisocyanate is considered to be aliphatic if its isocyanate groups are exclusively directly connected to aliphatic groups. Are the isocyanate groups with both aliphatic and cycloaliphatic Groups directly connected, it is an aliphatic-cycloaliphatic polyisocyanate.
  • Aliphatic, aiiphatic-cycloaliphatic, cycloaliphatic and aromatic polyisocyanates are preferably used.
  • aromatic polyisocyanates are preferably used when a certain tendency to yellowing can be accepted in the films according to the invention. However, if freedom from yellowing is very important, aliphatic, cycloaliphatic and aiiphatic-cycloaliphatic polyisocyanates are preferably used.
  • polyisocyanates are polyurethane prepolymers containing isocyanate groups, which can be prepared by reaction of polyols with an excess of aliphatic, aliphatic-cycloaliphatic, cycloaliphatic and aromatic diisocyanates and are preferably low-viscosity.
  • aromatic diisocyanates examples include 2,4- or 2,6-tolylidene diisocyanate, 1, 2-, 1, 3- or 1, 4-phenylene diisocyanate, 1, 2-, 1, 3-, 1, 4 or 1, 4 -Naphthylene diisocyanate or di (4-isocyanatopheny-1-yl) methane or propane.
  • 1, GB 1220717 A1, DE 16 18 795 A1 or DE 17 93 785 A1 preferably isophorone diisocyanate, 5-isocyanato-1- (2-isocyanatoeth-1-yl) -1,3,3-trimethyl- cyclohexane, 5-isocyanato-1- (3-isocyanatoprop-1-yl) -1, 3,3-trimethyl-cyclohexane, 5-isocyanato- (4-isocyanatobut-1-yl) -1, 3,3-trimethyl- cyclohexane, 1-isocyanato-2- (3-isocyanatoprop-1-yl) cyclohexane, 1-isocyanato-2- (3-isocyanatoeth-1-yl) cyclohexane, 1-isocyanato-2- (4-isocyanatobut-1- yl) -cyclohexane or HDI, especially HDI.
  • Polyisocyanates (B) containing isocyanurate, biuret, allophanate, iminooxadiazinedione, urethane, urea, carbodiimide and / or uretdione groups can also be used, which are prepared in a customary and known manner from the diisocyanates described above.
  • Examples of suitable production processes and polyisocyanates are, for example, from the patents CA 2,163,591 A, US-A-4,419,513, US 4,454,317 A, EP 0 646 608 A, US 4,801, 675 A, EP 0 183 976 A1, DE 40 15 155 A1, EP 0 303 150 A 1, EP 0 496 208 A 1, EP 0 524 500 A 1, EP 0 566 037 A 1, US 5,258,482 A 1, US 5,290,902 A 1, EP 0 649 806 A 1, DE 42 29 183 A or EP 0 531 820 A 1 or they are described in the unpublished German patent application DE 100 05 228.2.
  • polyisocyanates described in German patent application DE 196 09 617 A1 with polyisocyanates containing isocyanate-reactive functional groups, dioxolanes and oxazolidines, which still contain free isocyanate groups or are used in combination with other polyisocyanates, are suitable as polyisocyanates.
  • the content of polyisocyanates in the coating materials can vary very widely and depends on the requirements of the individual case, in particular on the content of isocyanate-reactive groups in the constituents.
  • the content is preferably 5 to 50% by weight, preferably 6 to 45% by weight, particularly preferably 7 to 40% by weight, very particularly preferably 8 to 35% by weight and in particular 9 to 30% by weight. %, each based on the solid of the coating material of the invention.
  • the repair paints contain components that make them radiation-curable.
  • Suitable radiation-curable constituents are the radiation-curable binders described above, as are used in the clearcoats.
  • the radiation-curable binders may also contain the isocyanate-reactive functional groups described above.
  • Suitable radiation-curable constituents are isocyanatoacrylates which contain groups containing double bonds and free isocyanate groups.
  • Suitable double bonds are, for example, in (meth) acrylate, ethacrylate, crotonate, cinnamate, vinyl ether, vinyl ester, ethenylarylene, dicyclopentadienyl, norbomenyl, isoprenyl, isoprenyl, isopropenyl, allyl or butenyl groups; Ethenylarylene, dicyclopentadienyl, norbomenyl, isoprenyl, isopropenyl, allyl or butenyl ether groups or ethenylarylene, dicyclopentadienyl, norbomenyl, isoprenyl, isopropenyl, allyl or butenyl ester groups.
  • (meth) acrylate groups, in particular acrylate groups are of particular advantage and are therefore used with very particular preference.
  • the isocyanatoacrylates can be prepared by reacting the above-described polyisocyanates with compounds which have an isocyanate-reactive functional group and at least one group containing double bonds.
  • suitable compounds of this type are 2-hydroxyethyl acrylate, 2- and 3-hydroxypropyl acrylate, 2-, 3- and 4- Hydroxybutyl acrylate, its reaction products with epsilon-caprolactone or allyl alcohol.
  • EP 0 928 800 A1 European patent application EP 0 928 800 A1.
  • the refinish paints can also contain at least one of the additives described in German patent application DE 199 20 799, page 7, line 6, to page 8, line 37.
  • Leveling agents are preferably added to the automotive refinish and clear coat in order to achieve good wetting behavior clear coat / color coat.
  • the pigmented lacquers which can preferably be used according to the invention include those which are curable thermally and by means of radiation (so-called dual cure systems).
  • the liquid paints are applied first. At this stage, they have a low viscosity.
  • Thermal curing creates an elastomeric coating that can be further crosslinked by subsequent crosslinking and exposure to radiation.
  • a polyurethane network can first be produced from the isocyanate acrylates described above and the binders containing hydroxyl groups, which is then crosslinked to give polyurethane polyacrylate under the action of radiation.
  • the layer thicknesses after stretching the topcoats used according to the invention are 10 ⁇ m to 60 ⁇ m, preferably 15 ⁇ m to 40 ⁇ m. Just like the layer thickness of the clear lacquers, the top lacquer layer thickness also depends on the chosen stretching.
  • Electron radiation and UV radiation are preferably used for the radiation curing of the clear lacquer layer and the pigmented layer. Curing with UV radiation is preferred according to the invention.
  • the combination of the properties of a conventional 2-component system with a UV-crosslinking system is particularly advantageous. Thanks to the behavior that is elastomeric at room temperature, very good thermoformability is achieved, while after exposure to radiation, good cross-linking is achieved at the seam to the clear coat.
  • the layers described in the combination of radiation-curable and at least partially radiation-curable layer according to the invention adhere particularly to one another, especially if the last-mentioned layer is a dual cure system. This liability is not lost even with thermal or mechanical influences.
  • carrier foils are used which preferably have a thickness of ⁇ 100 ⁇ m, particularly preferably a thickness of> 40 ⁇ m. Thicknesses of 50 ⁇ m to 70 ⁇ m are particularly preferred. 50 ⁇ m to 60 ⁇ m are very particularly preferred.
  • Polyester films with a thickness of 10 ⁇ m to 100 ⁇ m are preferably used here. 18 ⁇ m to 75 ⁇ m are particularly preferred.
  • the carrier film coated with the lacquers can be used to coat a wide variety of substrates. It is preferred according to the invention that the coloring layer is applied to the substrate. After complete curing by exposure to actinic radiation, the outer carrier film can be removed.
  • connection to the substrate can be made with adhesion promoters.
  • adhesives are preferably used. Again, it is preferred to use UV-curing adhesives. Here, UV radiation is preferably used to adjust the adhesive properties.
  • Adhesives of this type are commercially available products and are sold, for example, by BASF-Aktiengesellschaft under the Acronal ® 258 UV brand. In this case, the Adhesive layer applied to a separate film and after the UV coating on the top coat layer. This method is particularly advantageous if the top coat layer is a dual-cure system.
  • the adhesive properties can preferably be set here by pre-crosslinking using acetic radiation.
  • Adhesives suitable for this are described, for example, in Römpp Chemie Lexikon, 9th edition, volume 3, Georg Thieme Verlag, Stuttgart, 1990, "Adhesives", pages 2252 to 2255. Of these adhesives are the radiation-curable adhesives based on (meth) acrylates or UP resins (see Römpp Lexikon Lacke und Druckmaschinetician, Georg Thieme Verlag, Stuttgart, New York, 1998, "Unsaturated Polyester Resins", pages 591 and 592 , or D. Stoye and W.
  • the radiation curable adhesives may contain the radiation curable ingredients described above.
  • UV systems require reinforcement films coated on both sides.
  • Conventional pressure sensitive adhesives can be applied directly to the top coat.
  • the thickness of the adhesive is preferably between 4 ⁇ m and 20 ⁇ m.
  • the reinforcing film is preferably applied to the adhesive present on the pigmented lacquer layer. With appropriate Reactivity of the reinforcement film, for example through adhesion promoters, can be dispensed with on the adhesive layer.
  • the outer side of the reinforcing film is preferably in turn provided with an adhesive. This adhesive can be covered with a removable release film until processing.
  • this preferably has a thickness between 20 ⁇ m and 50 ⁇ m. 20 ⁇ m to 30 ⁇ m are particularly preferred. Polypropylene is preferred as the material.
  • An adhesive can be applied to the second layer of lacquer. This can be poured on, laminated or transferred. A further film with a preferred thickness of ⁇ 100 ⁇ m, preferably ⁇ 500 ⁇ m can be applied to this.
  • the lacquer film is cold-formable (deep-drawable) and can therefore be applied to any structured surface at room temperature or, if necessary, to make work easier with gentle heating.
  • the thermoformability of the films coated according to the invention is achieved if a further film is laminated onto the adhesive layer on the pigmented lacquer layer. These are regularly thicker films. Films according to the invention are preferred 300 ⁇ m to 1000 ⁇ m. 400 ⁇ m to 700 ⁇ m are particularly preferred. ASA, ABS, ASA-PC are particularly suitable for this.
  • Stable 3D structures can be produced from the composite by thermoforming. This requires effective drying of the laminate. The surface properties of gloss, metallic and flop effects are not affected by the deformation.
  • the present invention also relates to a method for producing the coated films mentioned.
  • the individual layers of lacquer can be applied either one behind the other or preferably by means of approximate simultaneous coating. In the latter method, the layers are applied directly wet in wet at short time intervals. The system is then thermally dried in a drying tunnel. In particular, this is intended to remove the solvent.
  • the coated films produced according to the invention can be used wherever painting of substrates is required.
  • substrates made of steel, aluminum and plastic can be coated.
  • the automotive industry is a preferred area of application.
  • the system according to the invention can also be used well for rail vehicles, ie locomotives and rail wagons.
  • the area of application includes accompanying strips to full paintwork.
  • Of particular advantage here is the possibility of removing the paint films again. In this way it is particularly easy to produce new partial paintwork on the vehicles.
  • the removability is also an advantage Vandalism, for example by smearing or spraying paint (graffiti). Protection of the lacquer surfaces can also be ensured by the carrier film until the end product is produced. Finished body parts can, for example, first be back-injected or back-foamed and the carrier film only removed after this process has been completed.
  • Figure 1 shows a layer structure of carrier film, clear lacquer and color lacquer and an adhesive.
  • Figure 2 shows a structure of a film coated according to the invention with reinforcing film.
  • Figure 3 shows a structure of a film coated according to the invention with particularly good thermoforming properties.
  • FIG. 4 shows an application process for the production of the films coated according to the invention.
  • the coated film 1 shown in FIG. 1 consists of a polypropylene carrier film 50 ⁇ m thick, a clear lacquer 2 40 ⁇ m thick and a color lacquer 3 30 ⁇ m thick, and an adhesive 4 20 ⁇ m thick. Tests have shown that the thermoformability of these coated films is excellent. At the same time, the thermal stability for production is sufficiently good. With a dryer gradient of 30 ° C / 60 ° C / 105 ° C results in good running and winding behavior in the coating machine.
  • FIG. 2 shows a polypropylene carrier film 1 ⁇ m with a thickness of 50 ⁇ m. Furthermore, a UV clear lacquer layer 2 40 ⁇ m thick, a color lacquer 3 30 ⁇ m thick and an adhesive 4 20 ⁇ m thick. A reinforcing film 5 of 25 ⁇ m to 50 ⁇ m is laminated on this adhesive 4. A removable release film 7 is then laminated using a further adhesive 6 having a thickness of 20 ⁇ m.
  • UV-acrylic adhesive (Acronal 248 UV, BASF) was used as adhesive 4 and 6.
  • substrates such as steel, aluminum, plastic and primed metal sheets at temperatures between -30 ° C and + 90 ° C.
  • the coated films were removable without cracks in the peeling
  • FIG. 3 shows a polypropylene film 1 with a thickness of 50 ⁇ m, a UV clearcoat 2 with a thickness of 40 ⁇ m, a color layer 3 with a thickness of 30 ⁇ m, an adhesive 4 and a film 8 with a thickness of 500 ⁇ m.
  • Luran S was used for this purpose according to the invention.
  • the protective film is preferably only removed after the deformation and radiation crosslinking.
  • the advantage of the present invention is therefore that the protective film provides scratch protection for the surface during transport and processing.
  • the protective film also has the advantage that no oxygen inhibition occurs during UV crosslinking.
  • FIG. 4 shows an example of the production of the films coated according to the invention.
  • the carrier film 1 delivered on the roll is guided under a pre-metered casting system 9.
  • this contains the departments 11 and 12.
  • the clear lacquer 2 is supplied via the department 11 via the department 12 to the color lacquer 3.
  • the clear lacquer 2 reaches the film 1 and the color lacquer 3 is applied virtually simulatan wet to wet via the department 12.
  • the film and layers of paint are then passed through a dryer 13.
  • the casting system can also consist of two casting heads connected in series but spatially separated.
  • the clear coat is applied to the film via the first coater.
  • the top coat is applied directly in the wet-on-wet process under the second pouring head.
  • KRRC processes or preferably pre-metered pourers or so-called knife pourers are used.
  • pre-dosed or preferably extrusion caster over a spreading lip to smooth the coating.
  • the coated film is fed for further processing.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention concerne des films recouverts d'au moins deux couches de peinture (2) (3). Selon cette invention, le film support (1) est recouvert d'au moins une couche de peinture (2) radiodurcissable et d'au moins une deuxième couche de peinture (3), pouvant durcir au moins partiellement sans rayonnement. Cette invention concerne également un procédé de production de ces films et leur utilisation dans le revêtement de substrats en acier, en aluminium et en plastique.
PCT/EP2002/009104 2001-08-20 2002-08-14 Films recouverts de peinture WO2003018214A2 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
US10/485,818 US7579082B2 (en) 2001-08-20 2002-08-14 Films coated with paint
EP02772152A EP1419017B1 (fr) 2001-08-20 2002-08-14 Films recouverts de peinture
AU2002336973A AU2002336973A1 (en) 2001-08-20 2002-08-14 Films coated with paint
DE50206328T DE50206328D1 (de) 2001-08-20 2002-08-14 Mit lack beschichtete folien
JP2003522718A JP4086111B2 (ja) 2001-08-20 2002-08-14 ラッカーで被覆されたフィルム

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10140769A DE10140769A1 (de) 2001-08-20 2001-08-20 Mit Lack beschichtete Folien
DE10140769.6 2001-08-20

Publications (2)

Publication Number Publication Date
WO2003018214A2 true WO2003018214A2 (fr) 2003-03-06
WO2003018214A3 WO2003018214A3 (fr) 2003-09-18

Family

ID=7696019

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PCT/EP2002/009104 WO2003018214A2 (fr) 2001-08-20 2002-08-14 Films recouverts de peinture

Country Status (10)

Country Link
US (1) US7579082B2 (fr)
EP (1) EP1419017B1 (fr)
JP (1) JP4086111B2 (fr)
KR (1) KR20040030067A (fr)
CN (1) CN1242853C (fr)
AT (1) ATE322349T1 (fr)
AU (1) AU2002336973A1 (fr)
DE (2) DE10140769A1 (fr)
ES (1) ES2260480T3 (fr)
WO (1) WO2003018214A2 (fr)

Cited By (5)

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WO2005053861A1 (fr) * 2003-12-01 2005-06-16 Basf Coatings Ag Couche de finition transparente thermodurcie, son procede de production et son utilisation
WO2006117091A1 (fr) * 2005-05-03 2006-11-09 Basf Coatings Ag Procede de fabrication de films possedant un revetement, films ainsi obtenus, ainsi que leur utilisation pour la fabrication de pieces moulees, destinees a etre utilisees en particulier dans la construction automobile
EP2911168A1 (fr) * 2014-02-19 2015-08-26 Huf Hülsbeck & Fürst GmbH & Co. KG Générateur d'id et système de contrôle d'accès
EP2565033B1 (fr) * 2011-09-01 2016-02-10 Senosan GmbH Corps composite
EP3945155A1 (fr) * 2020-07-31 2022-02-02 Huhtamaki Flexible Packaging Germany GmbH & Co. KG Structure en couches à aptitude améliorée au recyclage

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JPH0578440U (ja) * 1992-04-01 1993-10-26 大昭和精機株式会社 切削装置
DE10140769A1 (de) 2001-08-20 2003-03-06 Basf Ag Mit Lack beschichtete Folien
JP2003073229A (ja) * 2001-09-03 2003-03-12 Asahi Kasei Corp セルロースを含有するスプレー剤
DE10201420A1 (de) * 2002-01-15 2003-07-24 Basf Ag Strahlungshärtbare Beschichtungen mit verbesserter Haftung
DE10233521A1 (de) * 2002-07-23 2004-02-05 Basf Ag Strahlungshärtbare Lacksysteme mit tieftemperaturelastischer Unterschicht
DE10248270A1 (de) * 2002-10-16 2004-05-06 Daimlerchrysler Ag Lackfolie zum Aufbringen auf einem Bauteil
DE102004010787A1 (de) * 2004-03-05 2005-09-22 Basf Coatings Ag Verfahren zur Herstellung einer mehrschichtigen Folie F und ihre Verwendung
DE102004055363A1 (de) 2004-04-16 2005-11-10 Karl Wörwag Lack- Und Farbenfabrik Gmbh & Co. Kg Flexibler Schichtverbund mit einem Träger und einer darauf angebrachten Schicht härtbaren Lackes
US7390559B2 (en) * 2004-10-22 2008-06-24 Ppg Industries Ohio, Inc. Multilayer coating system
DE102005019721A1 (de) * 2005-04-25 2007-04-05 Decoma (Germany) Gmbh Bauteil
KR100597946B1 (ko) * 2005-06-22 2006-07-06 도레이새한 주식회사 후막 코팅층을 형성하는 방법
US20080210565A1 (en) * 2005-08-08 2008-09-04 Shou-Hui Chen Method of Surface Treatment for Metal and Nonmetal Surfaces
EP1937454B1 (fr) 2005-10-21 2016-05-25 Entrotech, Inc. Feuilles protectrices, articles et procedes associes
DE102006002595A1 (de) * 2006-01-18 2007-07-19 Tesa Ag Verfahren zur Herstellung von vielseitig einsetzbaren Kunststoffprodukten mit bevorzugt abriebfester Oberfläche
WO2009041964A1 (fr) 2007-09-25 2009-04-02 Entrotech, Inc. Films de remplacement de peinture, composites de ceux-ci, et procédés associés
KR100803178B1 (ko) * 2007-10-10 2008-02-14 (주)해빛정보 필터 자동검사 방법
US10981371B2 (en) 2008-01-19 2021-04-20 Entrotech, Inc. Protected graphics and related methods
DE102009010990A1 (de) * 2009-02-19 2010-08-26 Karl Wörwag Lack- Und Farbenfabrik Gmbh & Co. Kg Solarzellenmodul und Verfahren zu seiner Herstellung
CN104371508B (zh) * 2014-11-03 2016-09-28 苏州福斯特新材料有限公司 一种耐候涂层组合膜
CN118909561A (zh) 2016-09-20 2024-11-08 庞贝捷先进表面技术有限责任公司 具有减少的缺陷的涂膜贴花、制品和方法
DE102019217560A1 (de) 2019-11-14 2021-05-20 Loparex Germany Gmbh & Co. Kg Transferfolie zum Übertragen von Beschichtungsmaterialien auf Bauteile

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CA1338535C (fr) * 1988-09-27 1996-08-20 Godwin Berner Methode d'application d'un support en couche mince a un substrat en 3 dimensions
US6254712B1 (en) * 1998-12-08 2001-07-03 Avery Dennison Corporation Extrusion coating process for making high transparency protective and decorative films
DE19709467C1 (de) 1997-03-07 1998-10-15 Basf Coatings Ag Beschichtungsmittel sowie Verfahren zur Herstellung von Mehrschichtlackierungen
DE10140769A1 (de) 2001-08-20 2003-03-06 Basf Ag Mit Lack beschichtete Folien

Cited By (7)

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WO2005053861A1 (fr) * 2003-12-01 2005-06-16 Basf Coatings Ag Couche de finition transparente thermodurcie, son procede de production et son utilisation
WO2006117091A1 (fr) * 2005-05-03 2006-11-09 Basf Coatings Ag Procede de fabrication de films possedant un revetement, films ainsi obtenus, ainsi que leur utilisation pour la fabrication de pieces moulees, destinees a etre utilisees en particulier dans la construction automobile
CN101171113B (zh) * 2005-05-03 2010-12-01 巴斯夫涂料有限公司 带有涂层的片材的制造方法、所得片材、及其用于制造模制件，尤其是用在汽车构造中的用途
US7968199B2 (en) 2005-05-03 2011-06-28 Basf Coatings Ag Method for producing films having a coating the films obtained in this way and their use for producing molded parts in particular for use in automobile construction
EP2565033B1 (fr) * 2011-09-01 2016-02-10 Senosan GmbH Corps composite
EP2911168A1 (fr) * 2014-02-19 2015-08-26 Huf Hülsbeck & Fürst GmbH & Co. KG Générateur d'id et système de contrôle d'accès
EP3945155A1 (fr) * 2020-07-31 2022-02-02 Huhtamaki Flexible Packaging Germany GmbH & Co. KG Structure en couches à aptitude améliorée au recyclage

Also Published As

Publication number Publication date
US20040208998A1 (en) 2004-10-21
CN1242853C (zh) 2006-02-22
EP1419017A2 (fr) 2004-05-19
WO2003018214A3 (fr) 2003-09-18
DE50206328D1 (de) 2006-05-18
JP4086111B2 (ja) 2008-05-14
DE10140769A1 (de) 2003-03-06
ES2260480T3 (es) 2006-11-01
ATE322349T1 (de) 2006-04-15
EP1419017B1 (fr) 2006-04-05
US7579082B2 (en) 2009-08-25
JP2005500186A (ja) 2005-01-06
AU2002336973A1 (en) 2003-03-10
KR20040030067A (ko) 2004-04-08
CN1543379A (zh) 2004-11-03

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